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Issue 37, 2012
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Facile synthesis of rhodium and iridium complexes bearing a [PEP]-type ligand (E = Ge or Sn) via E–C bond cleavage

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Abstract

Rhodium and iridium complexes bearing a tridentate [PEP] type ligand ([PEP] = {o-(Ph2P)C6H4}2E(Me); E = Ge or Sn) were synthesized through the phosphine exchange reaction accompanied by selective E–C bond cleavage. The ligand precursors {o-(Ph2P)C6H4}2EMe2 (E = Ge or Sn) were readily obtained in excellent yields by treating {o-(Ph2P)C6H4}2Li with 0.5 equivalents of Me2ECl2. Tris(triphenylphosphine)rhodium(I) carbonyl hydride M(H)(CO)(PPh3)3 (M = Rh, Ir) cleaved one of the E–Me bonds of {o-(Ph2P)C6H4}2EMe2 exclusively to afford the trigonal bipyramidal (TBP) complexes, [PEP]M(CO)(PPh3). Square-planar rhodium complexes [PEP]Rh(PPh3) were also prepared from the reactions of tetrakis(triphenylphosphine)rhodium(I) hydride Rh(H)(PPh3)4 with {o-(Ph2P)C6H4}2EMe2. Further, the trans influence of group 14 elements E (E = Si, Ge, Sn) in [PEP]Rh(PPh3) is discussed in terms of the 1JRh–P coupling constants, indicating that E exhibited a stronger trans labilizing effect in the order Sn < Ge < Si.

Graphical abstract: Facile synthesis of rhodium and iridium complexes bearing a [PEP]-type ligand (E = Ge or Sn) via E–C bond cleavage

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Publication details

The article was received on 08 May 2012, accepted on 09 Jul 2012 and first published on 09 Jul 2012


Article type: Paper
DOI: 10.1039/C2DT30996C
Citation: Dalton Trans., 2012,41, 11386-11392
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    Facile synthesis of rhodium and iridium complexes bearing a [PEP]-type ligand (E = Ge or Sn) via E–C bond cleavage

    H. Kameo, S. Ishii and H. Nakazawa, Dalton Trans., 2012, 41, 11386
    DOI: 10.1039/C2DT30996C

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